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ANNALES

UNIVERSITATIS MARIAE CURIE-SKODOWSKA


LUBLIN POLONIA
VOL. LX, 14 SECTIO AA 2005

TAED IR studies of bleach activator


for peroxide-based detergents
J. Ryczkowski* and S. Pasieczna
Faculty of Chemistry, Department of Chemical Technology,
Maria Curie-Skodowska University,
pl. M. Curie-Skodowskiej 3, 20-031 Lublin, Poland
tel. +48-81 537-55-96; fax: +48-81 537-55-65;
e-mail: ryczkows@hermes.umcs.lublin.pl

In the present work IR studies are discussed. The studies concerned TAED
(tetraacetyl ethylenediamine) bleach activator applied for peroxide-based
detergents. It was stated that infrared spectra of the coloured TAED
granules available in the washing powders are of the same nature as the
spectrum of commercial chemical reagent, and there is no influence of the
colourant applied. Depending on the temperature treatment an alkaline
TAED solutions can undergo transformation and degradation. Moreover,
the presence of hydrogen peroxide in the alkalined TAED solution
accelerates its transformation. There can be observed TAED-inorganic
support interaction, which nature depends on the pH of the solution.

1. INTRODUCTION

It has long been established that peroxygen bleaches that generate hydrogen
peroxide in the wash (such as perborate and percarbonate) are excellent stain
removal and textile whitening agents and that they are less aggressive to fabric
dyes than chlorine bleaches.
Dissolution of sodium perborate or sodium percarbonate under alkaline wash
conditions leads to the formation of the perhydroxyl ion (OOH-) [1]:

*
Author to whom all correspondence should be addressed.
TAED IR studies of bleach activator for peroxide-based detergents 219

NaBO3.4H2O H2O2 + Na+ + BO2- + 3H2O (1)

2Na2CO3.3H2O2 2[CO3]2- + 4Na+ + 3H2O2 (2)

H2O2 + OH- H2O + OOH- (3)

The perhydroxyl anion is an effective bleaching agent at temperatures above


60oC, but is insufficiently active to be effective in washes at below this
temperature or in short wash cycles. However, the perhydroxyl ion can be made
to react with compounds to produce peroxygen bleaches that are effective at
lower temperatures. TAED is such a compound and is known as a perborate or
percarbonate bleach activator.
The TAED-system was described for the firs time in 1959 and has now been
used successfully in European heavy-duty detergents. TAED is produced on a
large industrial scale in a two-stage sequence from ethylenediamine and acetic
anhydride at 150oC (Figure 1) [2].

Fig. 1. Scheme of TAED production (Hoechst).

A continuous reaction procedure guarantees a product purity of more than 99%.


The water of reaction, which is the sole by-product, can be disposed of without
any problems in a biological clarification plant. TAED contains two active
groups, from which two molecules of oxidizing and disinfecting peracetic acid
are released in the presence of H2O2. Because of its low molecular weight of
228, 140 mg active oxygen are thus available per gram of the activator. From
environmental aspects, the biodegradability of a detergent additive is of critical
220 J. Ryczkowski and S. Pasieczna

importance. TAED is totally mineralized to the extend of more than 95% in a


clarification plant within 28 days. No stable metabolites are observed on
degradation.The N-C bond is not the cause of biological stability if it can
undergo biological hydrolysis [3,4].
To improve the performance of household detergents, manufacturers have
used sodium perborate as a bleaching agent together with a bleaching activator
(up to 2% in the detergent formulation) whose role is to permit the bleaching to
occur at lower temperature [5]. Among the bleaching activators, TAED is one of
the most widely used [6].
One mole of TAED reacts with two moles of the perhydroxyl anion
(nucleophilic attack) to form two moles of the effective peracetate anion and one
mole of the biodegradable by-product DAED (diacetyl ethylenediamine; Figure
2) [1,7,8]. The remaining two acetyl groups on DAED cannot be displaced by
peroxide in the wash bath. The perhydrolysis reaction is rapid under alkaline
conditions.

Fig. 2. Schematic reaction of TAED (Warwick International).

The optimum pH for bleaching activity of the TAED activated peroxygen


system is approximately 9.5. However, the bleach system will work effectively
over a fairly broad pH range (8.5 10.5). As a consequence of its inherent
reactivity, TAED is sensitive to oxidizing agents and hydrolysis under alkaline
conditions. Therefore, in order to prevent premature reaction with perborate or
TAED IR studies of bleach activator for peroxide-based detergents 221

moisture during storage of the detergent powder, the TAED should be suitably
protected by detergent compatible materials. For this reason producers supplies
TAED in granulated forms, e.g., product contains 92% (2%) active TAED
formulated as a coated/granulated product. The product has several colors
(mainly white, green, blue; Fig. 3) to choose depending on users choice
(Warwick International).
The chemical nature of the blue colorant is a copper phthalocyanine complex
CI (colour index) 74160 pigment blue 15 [9]. The green pigment is a similar
metal complex (polybromochloro copper phthalocyanine) CI 74265 pigment
green 36 [1].
According to the growing number of patents concerning its use in detergent
formulations, TAED will be found more often in detergents and therefore in the
natural media. In spite of its fairly low concentration in detergent formulations,
TAED and TAEDs by-products (e.g.: etylenediamine, acetic acid, TriAED -
triacetyl ethylenediamine) might have an impact on the environment. TAED is
very slightly lipophilic and TriAED (one of the most usual TAED by-product)
very hydrophilic. TriAED can therefore affect bacteria cells less than TAED.
TAED by-products could thus have less effect on aquatic life than TAED itself
[10].

a) b)

N
N
C C
C C Br5-6
C N N C
C N N C
N Cu N
N Cu N
C N N C
C N N C Cl 9-10
C C
C C N
N

Fig. 3. Structural formulae of the pigments which are present in the TAED granules:
a) pigment blue 15, b) pigment green 36 (Warwick International).

A collaborative study has been carried out concerning the IR


spectrophotometric determination of TAED in raw materials [11]. As a result it
was found the analytical transmission band (17062 cm-1) for the quantitative
determination of TAED. However, there is no other IR data characterizing this
popular nowadays compound. In this work a preliminary spectroscopic results
concerning TAED bleach activator are delivered.
222 J. Ryczkowski and S. Pasieczna

2. EXPERIMENTAL

White, granulated commercial chemical reagent (N,N,N,N tetraacetyl


ethylenediamine TAED) was supplied by Fluka Chemika. Its IR spectrum
serves as the base for subsequent experimental data obtained. Colored granules
(blue and green) from the commercial washing powders (mechanically isolated
from the powder mixture) available on the market were characterized (by means
of IR), too. Next part of investigations was devoted to the adsorption of TAED
from the alkaline solution on the inorganic oxides characterized by the different
IEPS - isoelectric point of the surface [12,13]: V2O5, SiO2, TiO2, ZrO2, ZrO2-La
(7 wt. % La2O3), -Al2O3, and La2O3. TAED solubility in water is up to 10-3
mol/l [5,9]. To increase the concentration, the appropriate amount of TAED,
calculated for 0.1 mol/l solution, was transferred to the measuring flask, diluted
in water, and alkaline by sodium hydroxide for complete dissolution. Resulted
pH solution was within the range as it is using washing powder during normal
washing procedure (pH ~9.5). Following, supports samples were impregnated at
room temperature (RT) by the alkaline TAED solution (0.5 h), dried in the oven
(100oC) and then analysed. FT-IR transmission spectra of the investigated
samples, pressed in KBr pellets, were recorded using Bio-Rad Excalibur
3000MX spectrometer. Win-IR Pro software was used to control the
spectrometer and to process data. Spectra were measured at RT at an 8 cm-1
resolution. The average of 1024 scans was used for the transformation.

3. RESULTS AND DISCUSSION

Commercially important imidic bleach activator (TAED) was not extensively


studied by IR. Its infrared spectrum is rich in well shaped bands (Fig. 4).
The most characteristic vibration at 1707 cm-1 can be attributed to C=O
stretching, known in the literature as an amide I band (1740-1670 cm-1) [14].
This one was described in the literature as a transmission band for the
quantitative determination of TAED [11]. Another significant vibration related
to C-N stretching, and known as amide III band (1235-1165 cm-1) is located at
1192 cm-1.
Figure 5 presents spectrum of the commercial chemical reagent compared
with the spectra of coated/granulated color product taken from the commercial
washing powders.
As seen, there is a good correlation between spectra. Moreover, there is no
influence of the colorants (Fig. 3), which are present in the color TAED
granules.
TAED IR studies of bleach activator for peroxide-based detergents 223

421
440
1955

940

760
1845
60

584
552
Transmission (%)

618
1422

1025
1433

979
1325
40

1269
1357
1382
1681

1192
1707

20

2000 1800 1600 1400 1200 1000 800 600 400


-1
Wavenumber (cm )

Fig. 4. Mid IR spectrum of TAED.

a)
Transmission (a.u.)

b)

c)

1800 1600 1400 1200 1000 800 600 400


Wavenumber (cm-1)

Fig. 5. FT-IR spectra of TAED as: a) chemical reagent, and colored granules from
washing powders, blue and green (b and c, respectively).
224 J. Ryczkowski and S. Pasieczna

The permission level of the copper in the washing powder is less than 1 ppm [2],
so the existing amount of the colorants is probably below the detection limit of
the spectroscopy technique applied. This is the reason that recorded spectra are
in good agreement.
As it was pointed out in the experimental section, TAED is slightly soluble in
water and is going hydrolysis process (favored in acidic medium) to form
TriAED (equation (4)) and DAED (equation (5)) [5]:
Ac2N(CH2)2NAc2 + H2O AcNH(CH2)2NAc2 + AcOH (4)
AcNH(CH2)2NAc2 + H2O AcNH(CH2)2HNAc + AcOH (5)
Separate experiment with isolated DAED show that it is inert. The low
reactivity of DAED is typical of amides and due to resonance stabilization of the
amide bond [7]. However, it was confirmed, that TAED in the presence of
iron(III) undergoes further degradation and photodegradation [7].
Prior to the adsorption experiments an alkaline TAED solution was subjected
to temperature treatment. An appropriate amount of the solution was evaporated
and remaining solid residues were measured in a transmission mode (Fig. 6).
- 1237

a)
- 1239
- 1344

b)
- 1297
- 1341
- 1492
- 1645 -1637
Transmission (a.u.)

- 1345

c)
- 1414
- 1572

- 1415
- 1488 - 1489

- 1345
- 1451

d)
- 1415
- 1575

- 1450
- 1578

- 1493

- 1416
- 1448
- 1578

1800 1700 1600 1500 1400 1300 1200


Wavenumber (cm-1)

Fig. 6. Transformed TAED* from the alkaline solution evaporated at: a) 30oC, b) 50oC,
c) 80 oC, and d) 95oC.
TAED IR studies of bleach activator for peroxide-based detergents 225

Depending on the temperature treatment an alkaline TAED solutions


undergo: transformation (Fig. 6a), partial degradation (Fig. 6b and c), and deep
degradation (Fig. 6d). According to equation (5) the product of TAED
transformation (here denoted as TAED*) should be DAED. An additional
experiments have been done. Saturated TAED aqueous solution was prepared
and divided into two parts. First one left unchanged, and the second was slightly
alkalined. Following both solutions (neutral and alkalined, respectively) were
treated by hydrogen peroxide, and left until there was not observed oxygen
formation. As before, an appropriate amount of the solutions were evaporated (at
30oC) and remaining solid residues were analysed (Fig. 7).
An addition of H2O2 to the neutral solution cause partial transformation of
TAED (compare Figs 4a and 7a). Observed changes in bands position and their
intensities allow to conclude that intermediate compound (Fig. 7a) is not an
initial TAED, and still it is not TAED*. The neutral TAED solution was
evaporated at 50oC, too. IR spectrum of solid residue (not presented here) was
similar to those presented in Figure 7a. This is an indication that neutral TAED
solution treated with hydrogen peroxide is not so sensitive for temperature
treatment. According to the equation (4) an intermediate product of TAED
partial transformation could be TriAED. Based on the IR results it can be stated
that the solid residue from the alkaline and H2O2 treated TAED solution (Figure
7b) are of the same nature as TAED* (Fig. 6a). In this case the presence of
hydrogen peroxide only accelerates the transformation. The only product of
TAED transformation can be DAED [1,7]. This means, that presented spectra
(Figs 6a and 7b), described as TAED*, should be characteristic for DAED.
Finally, samples of inorganic oxides characterized by the different IEPS
(starting from the lowest value) [12,13]:

V2O5 < SiO2 < TiO2 < ZrO2 < ZrO2-La < Al2O3 < La2O3 (6)

were impregnated by the TAED* solution, than dried and subjected to IR


analysis (Figs 8 and 9).
The obtained spectra were compared with the spectrum of TAED*. This
comparison allow to conclude if there is any interaction between adsorbed
TAED* and inorganic oxides surface. The characteristic of the recorded spectra
is changed with the increasing value of the IEPS. For the oxides with
IEPS = 1.8 3.0 (Fig. 8) there can be observed an interaction with the adsorbed
TAED*, then there is almost no interaction (IEPS = 6.6 7), and finally (IEPS
8) again appears. However, the latest one is weaker than the first one. This can
suggest three different modes of TAED* adsorption in which supports hydroxyls
(OH2+, -OH, O-) are involved:
226 J. Ryczkowski and S. Pasieczna

a)

- 1320

- 1238
- 1289
- 1367
- 1446

- 1238
Transmission (a.u.)

- 1561

- 1291
b)

- 1344
- 1653

- 1490
- 1648

- 1413
- 1574

1800 1700 1600 1500 1400 1300 1200


Wavenumber (cm-1)

Fig. 7. IR spectra of solid residues obtained after evaporation TAED solutions treated
with H2O2: a) neutral, b) alkalined.
- 1237
- 1289
- 1406

a)
- 1572

b)
Transmission (a.u.)

- 1638

- 1434

c)
- 1635

- 1574
- 1634

1800 1700 1600 1500 1400 1300 1200


Wavenumber (cm-1)

Fig. 8. IR spectra of TAED* adsorbed on: a) V2O5, b) SiO2, c) TiO2.


TAED IR studies of bleach activator for peroxide-based detergents 227

a)

b)

- 1410

- 1358
- 1568
Transmission (a.u.)

- 1352
- 1620
c)

- 1558

- 1412
d)
- 1637

- 1569
- 1634

- 1561

- 1462

1800 1700 1600 1500 1400 1300 1200


Wavenumber (cm-1)

Fig. 9. IR spectra of TAED* adsorbed on: a) ZrO2, b) ZrO2-La, c) Al2O3, d) La2O3.

a) OH2+ with C=O group (hydrogen bond for oxides characterized by low IEPS
value),
b) OH with the whole TAED* molecule (Van der Waals interaction for oxides
with the IEPS value around 7), and
c) O- with hydrogen (hydrogen bond for oxides characterized by IEPS value
8).
As far as the projection to environment is concerned, this work provides
information about the fate of TAED or more precisely its transformation by-
product TAED*. Adsorption phenomena, particular in an acidic aquatic
environments, can have an influence on the biodegradability of TAED*.
However, aquatic environments are open systems and other factors (e.g., the
presence of metal ions, photodegradation) can have a major impact on the
biodegradation process.
228 J. Ryczkowski and S. Pasieczna

4. CONCLUSIONS

In the present work there was shown mid IR spectrum of TAED. It was stated
that infrared spectra of the coloured TAED granules available in the washing
powders are of the same nature as the spectrum of commercial chemical reagent,
and there is no influence of the colourant. Depending on the temperature
treatment an alkaline TAED solutions undergo: transformation, partial
degradation, and deep degradation. An addition of hydrogen peroxide to the
neutral TAED aqueous solution causes its partial transformation. The presence
of H2O2 in the alkalined TAED solution accelerates the transformation to
TAED* (DAED). There can be observed TAED*-inorganic support interaction,
which is stronger in an acidic environment, weaker in an alkalic one, and very
weak in neutral.

Abbreviations used in the text:


CI colour index RT room temperature
DAED diacetyl ethylenediamine TAED tetraacetyl ethylenediamine
FT-IR Fourier transform infrared TAED* transformed TAED
IEPS isoelectric point of the surface TriAED triacetyl ethylenediamine
IR infrared

REFERENCES

[1] Warwick International, information booklet and private information.


[2] Hoechst, TAED, information booklet.
[3] P. Pitter, V. Sykora, Chemosphere, 44, 823 (2001).
[4] V. Sykora, P. Pietter, I. Bittnerova, T. Lederer, Wat. Res., 35, 2010 (2001).
[5] N. Brand, G. Mailhot, M. Bolte, Chemosphere, 34, 2637 (1997).
[6] L. Baini, G. Bolzoni, G. Carrer, E. Faccetti, L. Valtora, E. Guiati, C. Paccheti, C. Ruffo,
O. Cozzoli, L. Sedea, Riv. Ital. Sostanze Grasse, 69, 615 (1992).
[7] D. M. Davies, M. E. Deary, J. Chem. Soc. Perkin Trans. II, 1549 (1991).
[8] S. Effkemann, U. Pinkernell, U. Karst, Anal. Chim. Acta, 363, 97 (1998).
[9] The Merck Index, 13th Ed., Merck & Co., Inc., Whitehouse Station, NJ, 2001, No. 2546.
[10] V. Deluchat, S. Lacour, B. Serpaud, J.-C. Bollinger, Wat. Res., 36, 4301 (2002).
[11] C. Ruffo, O. Cozzoli, G. Bolzoni, G. Carrer, E. Faccetti, L. Valtora, M. Montessori, L. Sedea,
Riv. Ital. Sostanze Grasse, 68, 631 (1991).
[12] J. Ryczkowski, Catal. Today, 68, 263 (2001).
[13] J. Ryczkowski, Appl. Surf. Sci., (2005) in print.
[14] G. Socrates, Infrared and Raman Characteristic Group Frequencies. Tables and Charts, 3nd
Ed., John Wiley and Sons, Chichester, (2001).
TAED IR studies of bleach activator for peroxide-based detergents 229

CURRICULA VITAE

Janusz Ryczkowski. Born in Poland in 1959. Graduated from


Nicolas Copernicus University in Toru (1983). Received his
Ph.D. and D.Sc. degree (1992 and 2004, respectively) in physical
chemistry from the University of Maria Curie-Skodowska in
Lublin. He is an official correspondent for Applied Catalysis
News Brief (since 1994), member of Polish Chemical Society
(since 1984), Polish Catalysis Club (since 1993). Besides frequent
short visits, he also made long-term stay to Central Research
Institute of Chemistry of the Hungarian Academy of Sciences
(Hungary) and Ecole National Superieure de Chimie de Lille
(France). Within the Socrates Programme (Teaching Staff
Mobility) he has visited partner European universities with a series of lectures. Moreover,
he is a Faculty representative in the European Chemistry Thematic Network Association.
As for today he has been a reviewer of several papers submitted to leading scientific
journals. On the request of the Authorities of Quaid-i-Azam University (Pakistan) since
1994 eight times he was a reviewer of doctoral theses. Recently he was a reviewer of the
Polish Ph.D. thesis. His main field of interest is preparation of supported catalysts,
catalyst'
s modification, their characterization, and application of infrared spectroscopy
(including photoacoustic) in catalytic research. He published over 80 papers.

Sylwia Pasieczna was born in Lublin, Poland in 1974. She


studied chemistry at Maria Curie-Skodowska University,
graduated in 1998. She is a member of Polish Chemical Society
(since 1998) and Polish Catalysis Club (since 1998). At present
she is an assistant at the Department of Chemical Technology at
Maria Curie-Skodowska University in Lublin. Her main field of
interest is an application of different techniques in the area of
infrared spectroscopy for surface and catalysts characterization.

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